Organocatalytic carbon dioxide fixation to epoxides by perfluorinated 1,3,5-triols catalysts.

In order to improve epoxides conversion to carbonates by fixation of CO2 a new type of perfluorinated triol catalysts was developed. These simple acyclic scaffolds of enhanced acidity are efficient for catalysis through selective H-bonding activation of the epoxide. In combination with TBAI as co-catalyst, this useful transformation is performed under only 1 atmosphere of CO2 and between 30 to 80 °C. Both the 1,3,5-triol motif and the perfluorinated side chains are crucial in order to observe this epoxide opening under such mild conditions. In addition, the stereochemistry of the starting epoxide can efficiently be conserved during the carbonate formation.

Catalytic strategies towards 1,3-polyol synthesis by enantioselective cascades creating multiple alcohol functions.

This review highlights the different enantioselective catalyst-controlled cascades creating multiple alcohol functions through the formation of several carbon-carbon bonds. Through subsequent simple derivatization, these strategies ensure the rapid preparation of 1,3-polyols. Thanks to the use of efficient metal- or organo-catalysts, these cascades enable the selective assembly of multiple substrates considerably limiting operations and waste generation. For this purpose, several mono- or bi-directional approaches have been devised allowing successive C-C bond-forming events. The considerable synthetic economies these cascades enable have been demonstrated in the preparation of a wide variety of complex bioactive natural products, notably polyketides.

Strategic Stereoselective Halogen (F, Cl) Insertion: A Tool to Enhance Supramolecular Properties in Polyols.

To improve the supramolecular properties of organic compounds, chemists continuously need to identify new tools. Herein, the influence of the stereoselective insertion of halogen atoms (F or Cl) on different supramolecular properties is analyzed. Inserting anti-halohydrins in polyols considerably strengthens the H-bonding networks and other supramolecular interactions. This behavior resulted in improved anion binding, H-bonding catalysis, or organogel properties of the designed polyols with strong perspectives for applications in other classes of substrates.

Quinine-Catalyzed Asymmetric Synthesis of 2,2'-Binaphthol-Type Biaryls under Mild Reaction Conditions.

Simple quinine as an organocatalyst mediates the addition of various naphthols to halogenated quinones to afford non-C2 -symmetrical, axially chiral biaryl products, which are promising compounds as chiral ligands and organocatalysts. The rotational barrier required to have two distinct atropisomers has been evaluated in the products generated from the addition of naphthols to various quinones by means of DFT calculations and HPLC. The use of halogenated quinones as reagents was necessary to have configurationally stable enantiomeric products which can be obtained in good yield and stereoselectivity. These compounds have also been prepared in gram quantities and recrystallized to near enantiopurity.

Development of copper-catalyzed enantioselective decarboxylative aldolization for the preparation of perfluorinated 1,3,5-triols featuring supramolecular recognition properties.

Fluorine is able to confer unique properties to organic molecules but the scarcity of natural organofluorine sources renders the development of new synthetic methods highly desirable. Using a chiral BOX/Cu combination, enantioselective decarboxylative aldolization of perfluorinated aldehydes has been developed. Most notably, the reaction occurring under mild conditions and with high enantiocontrol can create ketodiols in one single synthetic operation, which are precursors of crucial perfluorinated 1,3,5-triols. In addition, the reaction performed with chloral, validates the proposed transition state model based on steric interactions and provides the first enantioselective synthesis of hexachlorinated ketodiol of great synthetic utility. The ability of perfluorinated 1,3,5-triols to form a central hydrogen-bonding framework allows strong coordination of anions and the chirality obtained through the catalyst-controlled synthetic sequence demonstrates the selective chiral anion recognition ability of polyols.

Modular Enantioselective Synthesis of an Advanced Pentahydroxy Intermediate of Antimalarial Bastimolide A and of Fluorinated and Chlorinated Analogues.

A short enantioselective catalytic synthesis of the key C15-C27 fragment of bastimolide A, a natural product showing promising antimalarial bioactivity, is disclosed. The strategic insertion of halogen atoms such as fluorine and chlorine by enantioselective organocatalytic halogenations allowed an excellent stereochemical control for the formation of complex acyclic fragments bearing up to four stereogenic centers. Furthermore, besides the formation of the 1,5,7,9,13-pentahydroxy fragment of the natural product, this strategy opens the route to the modulation of the bioactivity by halogenohydrins.